Disazo dye and process of preparing the same



nnaaao JU'TIE AND lt ltttltllfihd ti l? li l thlt dtTtitllitil filljltlllhl to addition to being" tast, have excellent tinctorial power.

The new dyed may he represented by the lit where. ll, lt and lit, represent aromatic radicals without a hydroxyl, amino or sub stituted'aminogroup attached to the nucleus, and R represents an aliphatic or an aromatic radical or a substituted aliphatic or aromatic radical, such as tor-example, methyl, ethyl,

phenyl, nitro phenyl, hydroxy phenyl or carhoay phenyl. I

Broadly stated, the process of preparing 5,", the new dyes involves diazotizing an aromatic ammo compound, coupling the diazo hodyto an aromatic compound which contains an amino group, but contains no hydroxyl group attached to the nucleus, treatlng the amino are compound with nitro benzoyl chloride,

reducing the nitro group of this condensation product, diazotizing the amino-benzoyl amino azo compound, coupling this diazo body to an aromatic compound which contains an amino 35 group but contains no hydroxyl group attached to the nucleus, and then treating with a carhorylic compound adapted to condense with the resulting amino disazo compound and form herewith a product containing two a acyl "roups. In case the diacyl compound thus tained contains an amino group, it may he diaaotiaed on the fiber and coupled to any suitable component.

The new dye compounds and their prepara tion can best be disclosed hy the presentation cl anumloer oi" examples of actual embodiments thereot. It is to he understood, ot course, that these examples are furnished he low by way ct illustration only, and that the e details ot procedure specified and therein llpplteationnled January ta, rant. aerial Ltte. ldlhlitt.

disclosed are susceptible of variation and substitution.

Example 1 303 parts of Q-naphthylamine-ti:8Tdisulphonic acid are diazotized in the usual way. To the diazo compound there are added 107 parts of rn-toluidine dissolved in dilute hydrochloric acid; the mineral acidity is then neutralized with sodium acetate. After three to four hours stirring at -25 t the coupling will be complete. litter acidifying with hydrochloric acid the amino azo compound is salted out and filtered. The paste is stirred up with 5000 parts of water and dissolved with 4:0 parts of sodium hydroxide. 53 parts of: sodium carbonate are now added and the solution is heated up to h0-85 (3., when 180 parts of p-nitrohenzoyl chlorideare added with rapid agitation. The condensation takes place prac- 'ticaily immediately, the condensation product being mostly precipitated out. ln order to reduce the nitro-henzoyl compound there is added at 85*90 G. a solution of 117 parts sodium sulphide (lla fi) The reduction will he complete after 10-15 minutes stirrin The amino-benzoyl compound, most of whic will he in solution, is precipitated out with salt and filtered. The paste is stirred up again with 6000 parts of Water, acidified with 280 parts of a 31% hydrochloric acid solution and diazotized at 30 t). by the addition of 69 parts 0t sodium nitrite. After two to three hours stirring the diazotization will be complete. To the diaao compound there is now added again a solution of 107 parts out m toluidine in dilute hydrochloric acid and the mineral acidity is neutralized with sodium acetate. The mixture is allowed to stir six to eight hours at 25-80 0., when the coupling will be complete. The charge is now made alkaline with sodium carbonate, heated up to 70 (1, precipitated with salt, and filtered. This amino disazo dye is soluble in water with a reddislrorange color, hut is very sensitive to acid. ln order to convert it into the benzoyl derivative the paste is dissolved in 10000 parts of water at -35 C.

.53 parts ot sodium carbonate and thereatter 141 parts of benzoyl chloride are added and the mixture is strongly agitated for about one hour. The color of the solution changes slowly from a reddish-orange to a bright yellow which does not change on spotting with acid. The dye is salted out'and filtered. In its dry ground form it is an orange powder, soluble in water with a bri ht yellow color, soluble in concentrated sulp iuric acid with a bright scarlet color. It dyes cotton in bright yellow shades which show good fastness to washing and an excellent fastness to light. Cotton-silk fiber is dyed in very uniform shades; Hydrosulphite will discharge the dye to a pure white. The dye has most probably the following formula:

SOsNe SOQN ride, the p-nitro-benzoyl derivative will be obtained, which shows again similar properties to the benzoyl compound. This nitroride and reducing with sodium sulphide as shown in Example 1, then diazotizing the amino-benzoyl compound and coupling it to 223 parts of l-napht-hylamine-6-sulphonic acid in the presence of sodium acetate, an intermediate d e is obtained which in the form of its so ium salt is soluble in water with a bluish-red coloration. This dye is dissolved in 10000 parts of water at -85 C., and after adding 53 parts of sodium carbonate condensed with 186 parts of p-nitrobenzoyl chloride, the nitro benzoyl derivative is then reduced at -90 C. with 117 parts of sodium sulphide and the aminobenzoyl derivative is salted out. This dye is soluble in water with a yellowish colora- N=NQNRCOON= Qmicoom c V CE:

tion; in concentrated sulphuric acid it gives a Bordeaux coloration. It dyes cotton in yellowish-orange shades, which may be diazotized and developed on the fiber. The beta-naphthol developed shade is an orangebrown; the pyrazolone shade is a bright yellowish-brown. All dyeings show an excellent fastness to light; the developed dyeings in addition to this are ver fast to washing. This dye has most probably the following formula:

benzol derivative may be reduced and thus converted to the p-amino-benzoyl deriva- SOaNa BOtN Using instead of 1303 parts of 2-naphthylamine-6:8-di'sul honic acid 173 parts of p-sulphan'ilfic acld, coupling this to m-toluidine, condensing with p-mtro-benzoyl chlo- N-NQNEOQ-O-N Example 3 303 parts of 2-naphthylamine-6 8-disulphonic acid are diazotized in the usual way.

This diazo compound is added to a solution mus acidity is neutralized with sodium hyliQN ECOONH:

droxide, and after the neutral reaction has been reached there are added 53 parts of sodium carbonate. The temperature is raised to "about 85 C. and 186 parts of p-nitro-benzoyl chloride are now added while agitating strongly. The nitro-benizo zoyl compound is salted out and filtered. The reduction, further diazotization, coupling to in-toluidine, and condensation with benzoyl chloride are carried out as described in Example 1. The shade of the benzoyl compound. is slightly redder than the dye of Example 1. On cottonsilk fiber it dyes silk weaker than cotton. The fastncss properties are similar to those of the dye in Example 1. The dye has most probably the following formula:

coma

SO Na some The corresponding p-amino-benzoyl compound instead of the benzoyl derivative shows on direct dyeings a similar shade to the benzoyl dye; the beta-naphthol developed dyeings show bright yellowish-orange shades; the pyrazolone developed shades are bright yellows.

Among other compounds which may be used as first components in addition to those named in the examples may be mentioned metanilic acid, aniline-disulphonic acid, the toliudinc sulphonic acids, the naphthylaminc sulphonic acids 2-naphthylaminel-:8- disulphonic acid, 2-napthylamine-3:6 and 3 S-disdlphonic acids.

Among other compounds which may be used as second and third components in addition to those named in the examples may he mentioned :-aniline, para xylidine, o-an isidine, alpha-naphthylamine, and 1-naphthylami'ne-7-sulphonic acid.

lit is apparent that, where the term radical is employed in the appended claims, either a substituted or an unsubstituted radical may be indicated.

lVo claim:

'l. A dye compound comprising the group:

in which R, R and R represent aromatic radicals having neither a hydroxy nor an emino group attached to the nucleus and COLL represents an acyl radical.

2. A. dye compound comprising the group: 1'

in which R, R and R represent aromatic radicals having neither a hydroxyl. nor an anime group attached to the nucleus and R represents an aromatic or an aliphatic radical.

3. The compound set forth in claim 2, wherein the disazo group contains at least one sulpl'ioni.c acid group;

4. The compound set forth in claim 2,

wherein the disazo group RN=N-R1-NH.CO.CUH4N=NILJ contains two sulphonic acid groups.

5. The compound set forth in claim 2 wherein the azo group RN=NR contains at least one sulphonic acid group.

(3. The compound set forth in claim 2 wherein the groups represented by R and TL each contain a sulphonic acid group.

7. The compound set forth in claim 2 wherein the groups represented by R and R each contain a sulphonic acid group.

8. The compound set forth in claim 2, wherein the groups represented by R and R each contain a sulphonic acid group.

9. The compound set forth in claim 2, wherein R represents an amino compound.

10. The compound set forth in claim 2, wherein R represents an aromatic amino compound.

11. The process of preparing a dye compound which comprises diazoting an aminobenzoylaminoczo compound containing no hydroxyl group or other free amino grou attached to the nucleus, coupling the resu ting diazo body to an aromatic compound containing an amino group but not containing a hydroxyl group and treating the resulting amino disazo compound with a carboxylic compound adapted to condense therewith and form a product containing an acyl group.

12. The process set forth in claim 11, wherein the amino-disazo compound contains at least one sulphonic acid group.

18. The proc ss set forth inclaiin 11, wherein the amino-disazo compound contains at least two sulphonic acid groups.

14. The process set forth in claim 11, Where in the amino-benzoylamino-azo compound contains two sulphonic acid groups.

15. The process set "forth in claim 11, wherein the'carlooiiylic compound is an aryl compound.

16. The process set forth in claim 11., wherein the carhonylic compound is an aryl nitro compound.

17'. The process set forth in claim 11, wherein the carhoxylic compound is nitro-benzoyl chloride and the nitro group of the resulting product after the condensation is reduced to an amino group.

In testimony whereof We allii; or signatures.

EMMET l HTTCH. HENRY J'OltlDnll. AUBREY U. BRADLEY. 

